Hydrogen elimination and thermal energy generation in water-activated chemical heaters

ABSTRACT

Less hazardous methods for generating thermal energy for heating water, medical supplies or comestible products using improved flameless chemical heaters/flameless ration heaters by novel chemical or electrochemical means, each capable of suppressing the generation of hydrogen gas. Remote unit self-heating meals may be more rapidly heated by forming a reaction mixture comprising magnesium or a magnesium-containing alloy, and a hydrogen eliminator or suppressor, and introducing water to react the reaction mixture and generate a more rapid release of thermal energy sufficient to effectuate a more accelerated temperature rise and more rapid heating of medical supplies, water, rations or other comestible substances while simultaneously suppressing or eliminating the generation of potentially hazardous hydrogen.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation-in-Part of application Ser. No. 12/069,995, filed on Feb. 14, 2008, which is a Continuation-in-Part of application Ser. No. 11/657,852, filed Jan. 25, 2007, which claims the benefit of Provisional Application Ser. No. 60/764,213, filed on Feb. 1, 2006, which applications are incorporated herein by reference.

BACKGROUND OF THE INVENTION

Flameless Chemical Heaters (FCH), also known as Flameless Ration Heaters (FRH), are used in Meal, Ready-to-Eat (MRE) packaging to provide hot meals to soldiers in the field or for warming or heating medical supplies or food rations in confined spaces (e.g., tents, underwater shelters) or in remote locations where there is no heat source. These FCHs or FRHs are generally based on the reaction of magnesium with water to form magnesium hydroxide and hydrogen which releases about 85 kcal of energy per mole of magnesium.

There are two types of MREs. The first is an individual meal for the soldier. The second one is a family-style meal for a group of 10-20 soldiers, called the Unitized Group Ration-Express (UGR-E). Both of these MREs use a Flameless Ration Heater (FRH) as the heat source for the hot meal. The temperature of a 250 gram individual MRE entrée can be raised by 100° F. in about 10 minutes using a 14 g FRH. Typically, the process of heating food consists of adding about 40 ml of water to the FRH by the military or other user, in order to activate the chemical reaction that produces the heat. Presently, the FRH consists of a magnesium, iron and salt mixture. The iron is used to activate the reaction of magnesium with water, whereas the salt prevents the formation of a magnesium oxide film on the magnesium metal surface. The reaction products are magnesium hydroxide and hydrogen. With the individual MRE, the liberation of up to 13 liters of hydrogen gas has not been a substantial safety problem.

The Unitized Group Ration-Express (UGR-E) is a complete meal in a box and can feed small groups of eighteen soldiers. Again, the food is heated by using a proportionally larger FRH that is activated by the addition or distribution of water. The problem associated with the release of hydrogen is significantly magnified with group meals. For a UGR-E weighing 28 pounds and requiring approximately 400 g of heater material, the amount of hydrogen released is typically 13.5 cubic feet or 380 liters. Thus, the concern is that generation of this large quantity of hydrogen in a confined space will exceed the Lower Explosive Limit of 4%.

Accordingly, there is a need for an improved system for the elimination, or at least minimization of hydrogen generation in magnesium/water based flameless heaters.

SUMMARY OF THE INVENTION

It is therefore a principal object of the invention to eliminate or suppress the cogeneration of hydrogen in all types of magnesium-based FCHs, to prevent the release of hydrogen into the atmosphere and preventing potentially explosive situations by means of a novel process.

Thus, one principal aspect of the invention includes useful methods for generating energy for flameless heating, such as for foodstuffs, water, medical supplies, etc., especially in the case of outdoor applications for camping, emergency, military applications all without the cogeneration of hazardous hydrogen by the steps of:

(i) forming a reaction mixture comprising at least magnesium or a magnesium-containing alloy and a hydrogen eliminator or suppressor, and

(ii) reacting the reaction mixture of (i) by introducing water to generate sufficient energy for heating an adjacently package substance or article, such as water, medical supplies, comestible substances, etc., while simultaneously eliminating or suppressing the cogeneration of potentially hazardous hydrogen.

This inventor discovered a new class of useful hydrogen suppressors or eliminators for flameless heaters.

Accordingly, it is still a further principal object of the invention to provide novel methods and compositions of matter for the flameless generation of thermal energy, including heater devices and meal, ready-to-eat packaged meals wherein the methods and compositions not only suppress or eliminate the cogeneration of potentially hazardous hydrogen, but surprisingly, were discovered to provide a substantially accelerated temperature rise for more prompt heating of the packaged meal compared to other state-of-the-art flameless chemical heaters.

Generally, for purposes of this invention the expression “hydrogen suppressor” as appearing in the specification and claims is intended to mean any metal-containing oxidizing agent that is suitable for at least minimizing, and more preferably, eliminating the cogeneration of hydrogen in the presence of magnesium or a magnesium-containing alloy. The metal of the metal-containing oxidizing agent, more specifically, is one having multiple valences, and includes as a preferred group, oxides of transition metals, such as manganese and/or oxides of ruthenium, and more particularly, manganese dioxide and ruthenium dioxide, to name but a few.

It should be understood, there are other representative examples of reactants in addition to oxides of manganese and ruthenium as hydrogen suppressors or eliminators, which when mixed with magnesium and reacted with water at least minimize, and more preferably totally suppress the cogeneration of hydrogen, while effectively generating the desired thermal energy. Generally, the useful hydrogen suppressors or eliminators are transition metal oxides that avoid the cogeneration of hydrogen in the reaction with magnesium or magnesium alloys. Representative examples include noble metals, such as platinum, iridium and rhodium. Other multivalent transition metal oxides include such members as iron, cobalt, nickel, silver, gold, tin, zirconium, hafnium, tantalum, lead, copper, and so on.

Useful magnesium-containing alloys for the above reaction mixture can also include at least one alloying element, such as iron, cobalt, nickel, zinc, aluminum and mixtures thereof.

The subject invention also contemplates optional additives in practicing the flameless heating methods disclosed herein comprising at least one member selected from hydrogen overvoltage suppressors, promoters, flowing agents and reaction activators.

As previously mentioned, it is still a further principal object of the invention to provide novel hydrogen suppressing or eliminating flameless, thermal energy generating chemical compositions. The compositions comprise reaction mixtures having at least: magnesium and/or a magnesium-containing alloy, a hydrogen suppressor or eliminator that when mixed with water will initiate the flameless heat generating reaction.

Generally, the reactants are present in proportional amounts sufficient to generate heat for promptly raising the temperature of substances, products or articles, such as water, medical supplies, consumable rations, and the like, to the desired temperature within a reasonable time period. As previously pointed out, it was surprisingly and unexpectedly discovered the novel hydrogen suppressor or eliminator compositions of the present invention provide a substantially accelerated temperature rise over known flameless heat generating compositions comprising magnesium and water.

As previously mentioned, the hydrogen suppressing or eliminating flameless heat generating compositions may have other optional reactants, such as a hydrogen overvoltage suppressors, reaction promoters, flowing agents and reaction activators.

In addition to magnesium metal, the hydrogen suppressing, flameless heat generating reaction mixtures may also be prepared from alloys of magnesium, prepared from alloying metals, such as iron, cobalt, nickel, zinc, aluminum and mixtures of the same. Such alloys are known among skilled artisans, and are commercially available through ordinary channels of commerce.

Besides magnesium, the flameless heat generating reaction mixtures, like the previously described methods, also comprise at least one hydrogen eliminator/suppressor, such as oxides of manganese and/or ruthenium, and more particularly, manganese dioxide and/or ruthenium dioxide in a sufficient amount to suppress the generation of hydrogen. This includes other transition metal oxides like those previously discussed in connection with the methods of the invention.

It is yet a further principal object of the invention to provide for heater devices, such as trays and pouches comprising the hydrogen suppressing, flameless, heat generating compositions, particularly for heating water, food rations, including medical supplies especially useful for camping and military applications. This is especially intended to include Meal, Ready-to-Eat military ration packaging comprising the above flameless heater devices.

BRIEF DESCRIPTION OF THE DRAWING

For a further understanding of the invention and its characterizing features reference should now be made to the accompanying drawings wherein:

FIG. 1 is a top plan view of a porous sealed packet of flameless heat generating composition of the invention with a portion of the porous sealed cloth removed to show the milled composition;

FIG. 2 is a partial isometric view of a flameless heater containment pouch of the invention with a portion of the front panel removed for an interior view of the pouch with the porous packet of heat generating powder and the food ration packet;

FIG. 3 is similar to that of FIG. 2, except the containment pouch has been placed in a containment box, and water is being introduced into the flameless heater containment pouch for initiating the generation of heat for heating the food packet in the pouch;

FIG. 4 is a side elevational view of the containment box with a sidewall of the box removed to show the arrangement of the flameless heater pouch with sealed food ration packet in the pouch like that of FIG. 3, and with water added, wherein the box is propped up at the open end to assure the water remains in contact with the porous packet of heat generating powder;

FIG. 5 is a plot illustrating the rate of temperature rise of the flameless heat generating composition of the invention relative to the rate of temperature rise of prior art composition;

FIG. 6 is a further plot of the rate of temperature rise of another embodiment of the flameless heat generating composition of the invention relative to the rate of temperature rise of a prior art composition;

FIG. 7 is a further plot of the rate of temperature rise of additional embodiments of the flameless heat generating composition of the invention relative to the rate of temperature rise of a prior art composition; and,

FIG. 8 is a further plot of the rate of temperature rise of yet another embodiment of the flameless heat generating composition of the invention relative to the rate of temperature rise of a prior art composition.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention relates to novel methods and reaction mixtures/compositions for the generation of flameless heat mainly without the co-generation of potentially hazardous hydrogen previously associated with prior art methods and compositions. The methods of the invention employ at least one transition metal oxide powder, such as an oxide of manganese and/or ruthenium, for example, mixed with powdered magnesium or magnesium-containing alloy to generate flameless heat, free of, or with minimal cogeneration of hydrogen. The methods of the invention can be demonstrated by the following representative reaction scheme:

Mg^(o)+2MnO₂+H₂O→Mn₂O₃+Mg(OH)₂+Δ

The reaction eliminates or suppresses hydrogen generation, or at least minimizes its cogeneration, while providing accelerated temperature rise over prior methods, i.e., more spontaneous heat generation than the known Mg+H₂O reaction, as will be demonstrated by the methods below currently used in flameless chemical heaters or flameless ration heaters. It may be noted that the addition of CuCl₂, NaNO₃, and trichloroacetic acid to magnesium were believed to eliminate the hydrogen evolution reaction. However, NaNO₃ and trichloroacetic acid are not effective in fully suppressing hydrogen generation, and CuCl₂ in the MREs is not acceptable because of environmental and health considerations.

The novel chemical compositions of the present invention react and generate sufficient heat for promptly heating water, medical supplies, consumable rations, and the like, without simultaneously generating hydrogen. Methods of the invention rely on a metallic element, e.g., magnesium or alloy thereof, a hydrogen suppressor or eliminator, and water, the latter of which acts as a reactant and a medium for the reaction. Generally, the hydrogen suppressor or eliminator is a transition metal oxide, and include inter-alia noble and non-noble metal oxides. Other useful representative oxides include PtO, IrO₂, RhO₂, Fe₂O₃, Co₃O₄, NiO, Ag₂O, Au₂O₃, CuO, TiO₂, ZrO₂, HfO₂, Ta₂O₅ and PbO₂.

Optional additives for the hydrogen suppressing flameless heat generating chemical compositions and methods may include a hydrogen overvoltage suppressor, a promoter, flowing agent, activators, and the like.

The metallic element in the chemical composition that generates heat is magnesium or magnesium alloy containing from about 0.001% to about 10% iron, cobalt, nickel, zinc, aluminum, either singly or in combination with each other. A preferred composition is pure or substantially pure magnesium with small or trace amounts of other metals, e.g., <0.001% to about 0.1% of the alloying elements, iron, cobalt, nickel, zinc and aluminum. One preferred hydrogen suppressor in the chemical composition is MnO₂ and RuO₂. A preferred hydrogen suppressor may be either γ-MnO₂ or β-MnO₂, both known oxides, made either electrolytically or chemically by known methods, or from a naturally occurring ore that is treated. The amount of MnO₂ in the chemical composition is in ranges from about 1 to about 10 times the stoichiometric amount required for the Mg+MnO₂ reaction with water, the preferred amount being 1-10 times the stoichiometry.

The hydrogen overvoltage suppressor in the chemical composition may be a metal sulfide, the metal preferably being Fe, Co, Ni, or a highly electrically conductive carbon, present in amounts ranging from about 0.001 to about 1%. The promoter in the chemical composition is preferably a carbon in particulate or powder form, present in an amount ranging from about 0.001 to about 20 percent-by-weight. The filler or flowing agent includes such representative members as silicon dioxide and calcium carbonate, and is present in an amount ranging from about 0.001 to about 10 percent-by-weight. They are effective in also promoting the reaction rate of the flameless heater reaction mixtures. Activators for the reaction mixtures include alkali metal halides, such as NaCl, magnesium halide salts, such as MgCl₂, MgBr₂, including Mg(ClO₄)₂, and so on. Additionally, activators for the reaction mixtures include thermally and electrically conducting, high surface area synthetic graphite and other conducting carbon materials. An example of a suitable synthetic graphite includes Asbury 4827, produced by Asbury Graphite Mills, Inc., of Asbury, N.J., while suitable conducting carbons include Asbury TC 307, also produced by Asbury Graphite Mills, Inc., KETJENBLACK® (such as EC600JD), produced by Akzo Nobel Polymer Chemicals LLC, of Chicago, Ill., BLACK PEARLS® 2000 or 1300, both produced by Cabot Corporation, Alpharetta, Ga. The amount of activator can vary in the range from about 0.001 to about 50%. One preferred activator is MgCl₂, the other being electrically conductive carbon.

The reaction scheme set forth supra is an electrochemical corrosion reaction, the anodic reaction being the oxidation of Mg to form Mg²⁺ ions, the cathodic reaction being the reduction of MnO₂ to Mn₂O₃ and the electron transfer processes proceeding on the surface of MnO₂. It is for this reason that there is no need for a conducting electrolyte, such as a salt solution, to activate the reaction described supra. However, Mg is prone to form MgO and therefore, the reaction described supra does not proceed to completion unless an electrically conducting material such as carbon is added to the Mg/MnO₂ mixture and blended thoroughly to establish/provide good electrical connectivity between MnO₂ and Mg sites.

MgCl₂ serves the same purpose but in a different way. Thermodynamic potential-pH diagrams for an Mg/water system at various temperatures show that the pH at which Mg²⁺ is in equilibrium with Mg(OH)₂ shifts to lower pH values as the temperature increases. Thus, when MgCl₂ is added, the temperature rises to as high as 120-150° C., and facilitates the solubility of Mg(OH)₂ at pH=7, which is the pH of the water added to the reactants. Note that at pH=7 and at 25° C., the stable species is Mg²⁺, whereas at pH=7 and at 90° C., there is an equilibrium between these two species. This is the reason why addition of MgCl₂ promotes the accessibility of the blocked MgO sites. The pH value at which Mg²⁺ is in equilibrium with Mg(OH)₂ is strongly dependent on the activity of Mg²⁺ ions in the solution. It has been found that the higher the activity, the lower the pH value. We generally added MgCl₂ corresponding to an activity of >>1.

It will be understood, activators, e.g., MgCl₂ and carbon, may be introduced into the flameless heater compositions of the invention by various methods. For example, one method provides for blending/mixing an activator, such as MgCl₂ or and/or carbon in particulate form into the milled magnesium and hydrogen suppressor or eliminator when preparing the reaction mixture, before introducing the water reactant. Alternatively, an aqueous solution of the MgCl₂, e.g., 5 to 7 M solution of the activator in the water reactant (45 to 60 wt % solution), can be prepared and introduced together as a salt solution into the milled Mg and hydrogen suppressor or eliminator reaction mixture. However, the former method of blending the activator with the milled Mg and hydrogen suppressor or eliminator is generally more preferred because it is more effective in suppressing hydrogen than the latter method.

Example 1

In order to demonstrate the details of the invention based on a Mg/MnO₂+H₂O system according to the equation [1] below, the following experiment was conducted:

Mg+2MnO₂+H₂O→Mg(OH)₂+Mn₂O₃  [1]

A 99.98% pure Mg metal sample of 500% particle size from Superior Metal Powders, Franklin, Pa., was used in this test, and contained trace amounts, i.e., 85 ppm Al, 4 ppm Cu, 300 ppm Fe, 250 ppm Mn, 50 ppm Na, 150 ppm Si, 100 ppm Zn and 50 ppm Ca. In addition, a 300% size γ-MnO₂ powder from Tronox, LLC, Henderson, Nev., was used with a purity of 99%. The γ-MnO₂ contained trace amounts, i.e., 8600 ppm S, 2600 ppm Ca, <100 ppm Mg, <1000 ppm Al, <100 ppm Si, <100 ppm Cl, 700 ppm K, <1000 ppm Cr and <100 Sn ppm.

The above Mg and γ-MnO₂ powders were used to make a batch sample in a stoichiometric ratio according to equation [1], above. Approximately 500 g of the 300% particle size MnO₂ and 69.44 g of 500μ Mg were combined and placed in a mill. In this case the mill was a Vibrokinetic Energy (VKE) Mill, from Microgrinding System, Inc., Little Rock, Ark., model 624 (diameter=6″ and tube length=24″). This mill was operated with 36 stainless steel rods (6 with a diameter=1″, 30 with a diameter= 7/16″) with a length of 24″. The sample mixture was introduced into the mill via a 2″ diameter feed. All the screws and openings were tightened and secured prior to running the mill for 6 hours. At the end of the 6 hour milling period, the sample remained in the mill over night to cool. The sample was removed with a Nalgene scoop, transferred to a 600 ml stainless steel beaker and stored in a desiccator with calcium sulfate as the dehydrating agent.

Following FIG. 1 of the drawings, polypropylene bag 10 was fabricated from porous filter cloth 12 (Unilayer 270), available from Midwest Filtration Company, Cincinnati, Ohio. The filter cloth was a 6-ply sonic bonded polypropylene laminate having a thickness of 22 mils (0.5588 mm), a weight of 91.6 g/m², an air permeability of polypropylene 635 l/m²/sec and a Mullen Burst strength of 80 psi. The porous filter cloth fabricated from polymeric fibers allows the transmission of water, and the release of gases while precluding the blockage of pores by the solid reactants and/or products owing to its depth loading characteristics. An 8″×11″ sheet of the filter cloth was used to fabricate bag 10 for containment of milled Mg/MnO₂ reaction mixture 20 supra. It should be appreciated that as described infra bag 10 may be constructed in a variety of ways. For example, filter cloth 12 may be constructed from a single layer of 6-ply sonic bonded polypropylene laminate as shown in FIG. 1, or filter cloth 12 may be a dual layer bag consisting of two different filter cloth materials such as polyester fibers for one layer and polypropylene fibers for another layer, and either layer may be the inner or the outer layer of bag 10. Additionally, filter cloth 12 may be constructed from multiple layers of polyester fibers, e.g., four to six layers, or may be constructed as a dual composite fabric consisting of an inner layer of spunbond/meltblown/spunbond filter media containing 100% polypropylene and an outer layer of a 3-ply bonded polypropylene fiber cloth. An example of such an inner layer is Unipro 260-SMS which is made of white spunbond/meltblown/spunbond filter media containing 100% polypropylene with a thickness of 19 mils (0.4826 mm) and a weight of 2.60 oz/yd² (91.96 g/m²), with an air permeability of 17.1 cfm/ft² (86.9 l/m²/sec) and a Mullen Burst of 71 psi. It should further be appreciated that the foregoing examples are within the spirit and scope of the claimed invention.

First, filter cloth 12 was cut into a 6″×8″ sheet. The filter cloth was then made hydrophilic. One of two procedures and surfactants may be used in making the porous filter cloth hydrophilic. One method employs a “dip and nip” technique. This method requires taking the porous hydrophobic cloth and dipping it into a 5% aqueous solution of surfactant. The excess surfactant is then squeezed off by passing the cloth through a pair of nip rollers. The second method provides for applying a dab of Pluronic-25R2 surfactant, from BASF Corp., Florham Park, N.J., on one or both sides of the cloth.

Hydrophilic porous filter cloth 12 was then fabricated into bag 10 by folding the treated 6″×8″ sheet in half. The bottom 4″ of side 14 and 6″ of side 16 were heat sealed to form the pocket or bag 10 with opening 22 on the top 4″ of side 18 left open to allow for filling before applying the final heat seal. The heat seals were made using a Uline 8″ impulse Sealer (H-163). 100 g of the milled and dried Mg/MnO₂ powder 20 described supra was then placed in the Unilayer 270 polypropylene bag 10 and opening 22 on the top sealed closed. This sealed flameless ration heater reaction mixture bag 10 was then placed in green non-porous “poly” bag 24 (FIG. 2) having bottom closure seal 26 and upper opening 28. Poly bag 24, fabricated with a polypropylene film, had a capacity sufficient for also holding 250 g of water as “water test pouch” 30 used as a surrogate for a regular food ration packet. Poly bag 24 containing the reaction mixture bag 10 and water test pouch 30 were placed in “chipboard box” 34 (FIG. 3).

60 ml of water 31 (FIG. 3) were then added to green poly bag 24 on the same side as the ration heater and the top of bag 24 was folded over (not shown). The green poly bag, and its contents in “chipboard box” 34 (FIG. 4) were held substantially horizontally with the ration heater/reaction mixture bag 10 below water test pouch 30. After 30 seconds, the system was set at a slight incline (FIG. 4), to prevent water loss, and allowed to react for 30 minutes. The temperature variation was recorded as a function of time and shown in FIG. 5, and tagged “Present Invention Example 1”.

Example 2

In order to compare the performance of the hydrogen suppressing, flameless heat generating composition of the invention prepared according to Example 1, a second sample of the known flameless heat generating composition comprising Mg and H₂O only was prepared.

8 g of 500μ Mg/Fe, from Innotech Products, Inc., Cincinnati, Ohio as presently used in a U.S. Army ration heater, was prepared according to the recipe in U.S. Pat. No. 5,611,329. This sample was placed in a “non-woven” bag material from Innotech Product, Inc. The Innotech bag material was a roll configured into four, 1″ compartments distributed through the length of the roll. 6″ of this material was cut from the roll and the bottom was heat sealed with a Uline, 8″ impulse sealer (H-163). Each of the four compartments was filled with 2 g of the Mg/Fe and the ration heater was heat sealed closed (not shown).

The completed flameless ration heater was placed in a green polyethylene bag, from the U.S. Army, with a 250 g water pouch. After thirty seconds, 40 ml of an aqueous solution of 0.25 M sodium chloride was poured between the water pouch and the flameless ration heater. The top of the green bag was folded over and the green bag with its contents was placed in a “chipboard” box (not shown). For approximately 30 seconds, the box system was held horizontally with the ration heater at the bottom. Then, the system was set at a slight incline to prevent water loss, and allowed to react for 30 minutes. The temperature variation was recorded as a function of time and shown in FIG. 5, tagged as “Prior Art Example 2”.

FIG. 5, which plots test pouch temperature relative to time (minutes), demonstrates a significantly faster and higher (steeper) heat elevation temperature occurring with the flameless heating Mg/Mn oxide reaction mixture prepared according to Example 1 of the present invention relative to the known flameless heater composition of the prior art employing Mg/Fe reaction mixture without transition metal oxide (Example 2).

Example 2A

100 g of 500μ Mg/Fe, from Innotech Products, Inc., Cincinnati, Ohio as presently used in a U.S. Army ration heater, was prepared according to the recipe in U.S. Pat. No. 5,611,329. This sample was placed in an 8″×11″ bag made from the “non-woven” bag material from Innotech Product, Inc., that was configured into four, 2″ compartments distributed through the length of the roll. Each of the four compartments was filled with 25 g of 500% Mg/Fe and the ration heater was heat sealed closed.

This completed ration heater was placed in a UGR-E heating tray, over which a 3500 g “water pouch” was placed. This assembly was placed in a card board box and then 330 ml of 1.5% NaCl solution was added. The card board box was then closed and the edges sealed with a tape. The temperature variation was recorded as a function of time over a 60 m period, and shown in FIGS. 7 and 8, tagged as “Prior Art Example 3”.

Example 3

In order to demonstrate a further embodiment of the subject invention which includes a metal halide activator, a further experiment was performed with the reactants: Mg+MnO₂+MgCl₂ by means of the following protocol.

The milling procedure for the Mg/MnO₂ mixture was the same as that stated in Example 1. 45 g of the milled Mg/MnO₂ mixture was mixed with 15 g of 325 mesh MgCl₂, from Sigma-Aldrich, Inc., St. Louis, Mo. This Mg/MnO₂/MgCl₂ mixture was placed in a dual layer bag consisting of two different filter cloth materials made of polyester fibers (Finon C305NW) and polypropylene fibers (Unilayer 270). Finon C305NW is made of polyester fibers with a thickness of 7 mils (0.1778 mm) and a weight of 50.9 g/m², with an air permeability of 1,778 l/m²/sec and a Mullen Burst of 50 psi. This dual layer configuration is essential with Mg/MnO₂/MgCl₂ mixtures to provide thermal stability to the bag via the polyester fabric and the depth loading characteristic via the polypropylene, 6-ply, Unilayer. Both of the bag materials from Midwest Filtration were received in 8″×11″ sheets and cut into 6″×8″ sheets. To make these materials hydrophilic, the “dip and nip” process of Example 1 was employed. To configure the pouch, the Finon polyester material was placed aside the smooth surface of the Unilayer polypropylene and both are folded in half to make a 4″×6″ pouch with the polyester inside the Unilayer polypropylene (not shown). A Uline 8″ impulse Sealer (H-163) was used to heat seal the two materials together. The 6″ side, parallel to the fold and one of the 4″ sides were sealed prior to adding the reaction mixture. An additional seal, parallel to the 6″ side and down the center of the pouch was also added to make the pouch into two compartments. 30 g of the Mg/MnO₂/MgCl₂ mixture was added to each of the compartments. The pouch was heat sealed closed and placed in a green “polybag” with a 250 g water test pouch as a surrogate for a ration. 40 ml of water was added to the green bag on the same side as the ration heater. The top of the bag was folded over and the whole system was placed in a “chipboard” box. For approximately 30 sec, the box was held horizontally with the ration heater under the water pouch. Then the pouch was set at a slight incline for thirty minutes, as in Example 1. The temperature variation was recorded as a function of time and shown in FIG. 6, and tagged “Present Invention Example 3.”

The performance of the FRH composition of the “Present Invention Example 3” was also tested relative to the “Prior Art Example 2” with the results demonstrated by FIG. 6 of the drawings.

FIG. 6 illustrating the performance of the FRH composition of the present invention (Example 3) comprising Mg and MnO₂, plus MgCl₂ activator also provided a significantly faster and higher (steeper) rise in the generation of thermal energy relative to the known flameless heater composition of the prior art employing Mg/Fe reaction mixture without transition metal oxide (Example 2).

Bag Materials

As described above, bag 10 may be constructed in a variety of ways. As set forth in Example 1, bag 10 may be fabricated from porous filter cloth, such as Unilayer 270. In this example, the filter cloth is a 6-ply sonic bonded polypropylene laminate. Additionally, as set forth in Example 3, a dual layer bag consisting of two different filter cloth materials may be fabricated from polyester fibers, such as Finon C305NW, and polypropylene fibers, such as Unilayer 270. Furthermore, it has been found that bag 10 may also be fabricated from multiple layers, e.g., four to six layers, of polyester fibers, such as Finon C305NW. Similar to the previously described fabrications, the multiple layers can be sonically bonded and made hydrophilic by the “dip and nip” process of Example 1. Each of these fabrications provides varying levels of thermal stability and depth loading capability so that fine particles are prevented from blocking the pores and preventing entry of water from outside to the reactants inside the bag material. In the dual layer configuration, the polyester fiber provides thermal stability to the bag while the polypropylene provides the depth loading characteristic. Moreover, porous filter cloth fabricated from polymeric fibers allows the transmission of water, and the release of gases while precluding the blockage of pores by the solid reactants and/or products owing to its depth loading characteristics.

It has been found that with when Unilayer-based ration heater pouches are used in combination with the present invention, a very small seepage of carbon and/or MnO₂ fines occurs before and after the reaction. Such leakage leads to an unappealing aesthetic appearance of the heater and stains the hands of the person handling the heater. It has been found that these issues may be eliminated by employing a dual composite fabric consisting of an inner layer of 1.5 oz, Unipro 260-SMS (spunbond/meltblown/spunbond filter media containing 100% polypropylene), and an outer layer of Unilayer 135 which is a 3-ply bonded polypropylene fiber cloth. The temperature-time profiles of the present invention in combination with the Unilayer 270 and the Unilayer 135/Unipro-SMS arrangements described above are shown in FIG. 7 and labeled “Unilayer 270” and “Unilayer 135+Unipro-SMS”, respectively. The foregoing examples depicted in FIG. 7 are shown with an UGR-E heater, and the test procedure is set forth in Example 20 below. A prior art example is also shown in FIG. 7 and labeled “Prior Art Example 3”. It has been found that use of the above described Unilayer 135/Unipro 260-SMS fabric not only improved the heating rate, but also effectively precluded leakage of carbon and/or MnO₂ fines.

Hydrogen Generation

The amount of hydrogen generated by the FRH reaction mixtures of the present invention (Examples 1, 3 and 20) was measured on a comparative basis with the FRH reaction mixture of the prior art (Example 2) by collecting off-gases and analyzing for hydrogen content by means of gas chromatography. The results are provided in Table 1 below:

TABLE 1 Example Solid Reactants Liquid Reactants Hydrogen Suppression  1 Mg/MnO₂ Water 99%  2* Mg/Fe Water + NaCl** 0%  3 Mg/MnO₂/MgCl₂ Water 94% 20 Mg/MnO₂/C Water 97.1% 99.7% 20*** Mg/MnO₂/C Water + NaCl 98.9% *Results same as Mg/Fe/NaCl (0.6 g) + Water **Water containing 40 g H₂O + 0.6 g NaCl ***Same composition as Example 20, however liquid reactant is water having 1.5% NaCl

Example 4

The following example demonstrates the method for removing residual moisture (3.3% H₂O) from electrolytic manganese dioxide to near zero level for improving useful shelf-life of the reaction mixture.

In performing the process, 500 g of MnO₂ is placed in an oven set to 400° C. for 2 hours and then heated at 110° C. for 24 hours. This MnO₂ sample is mixed with Mg powder and milled following the procedure disclosed in Example 1. The remaining steps of the process correspond to those disclosed in Example 1, containing Mg+MnO₂.

Example 5

The following example demonstrates the method for removing residual moisture (3.3% H₂O) from electrolytic MnO₂ to near zero level in preparing a reaction mixture comprising Mg and MnO₂ (water-free), Plus MgCl₂ activator for improving useful shelf-life of the reaction mixture.

In performing the process, 500 g of MnO₂ is placed in an oven set to 400° C. for 2 hours and then heated at 110° C. for 24 hours. This MnO₂ sample is then mixed with Mg powder and milled following the procedure in Example 1. The remaining steps of the process are the same as those disclosed in Example 3, containing Mg+MnO₂+MgCl₂.

Example 6

The following example was performed to demonstrate the procedure for preparing a homogeneous reaction mixture that maximizes electrical contact of all the MnO₂ with Mg in the reaction mixture.

In performing the process, 300 g of 60μ γ-MnO₂, from Tronox, LLC, was mixed with the Mg powder and milled according to the procedure in Example 1. The remaining process steps corresponded to those disclosed in Example 1.

Example 7

The following example was performed to demonstrate the procedure employed in preparing a reaction mixture comprising Mg+MgCl₂ with small particle size (60μ) MnO₂.

In performing the process, 300 g of 60μ γ-MnO₂, from Tronox, LLC, was mixed with Mg powder and milled following the procedure in Example 3. The remaining steps are the same as that described in Example 3.

Example 8

The following example demonstrates preparation of a reaction mixture according to present invention comprising magnesium with manganese dioxide except with very small average particle size of 0.8μ.

In performing the process, 300 g of 0.8μ MnO₂ available from Sigma Aldrich can be mixed with Mg powder and milled following the procedure in Example 1, above. The remaining steps of the process can follow those disclosed in best mode Example 1.

Example 9

The following example also demonstrates preparation of a flameless heater reaction mixture according to the present invention, but with ultra fine particulates of MnO₂ (0.8μ γ-MnO₂) hydrogen suppressant, plus MgCl₂ activator.

In preparing the reaction mixture, 300 g of 0.8μ MnO₂, from Sigma Aldrich, is mixed with Mg powder and milled following the procedure of Example 3, above. The remaining steps for preparation of the reaction mixture correspond to those also described in best mode Example 3.

Example 10

The following best mode example also demonstrates a further aspect of the invention except the improved flameless heater composition is prepared with two (2) times the stoichiometric amount of manganese dioxide.

In preparing the composition, 600 g of MnO₂ from Tronox, LLC, is mixed with Mg particles and milled as described in working Example 1, supra. The remaining steps correspond to those also described in Example 1.

Example 11

The following best mode example also demonstrates a further aspect of the invention for preparing flameless heater compositions prepared with two (2) times the stoichiometric amount of manganese dioxide in combination with magnesium chloride activator.

In preparing the reaction mixture/composition, 600 g of MnO₂ from Tronox, LLC, is mixed with the Mg particles and milled in Example 1. The remaining steps correspond to those also described in Example 3.

Example 12

The following example demonstrates a further alternative embodiment of the invention comprising for Mg+MnO₂+1% Zn^(o) metal, wherein an additional alloying metal, i.e., zinc, is introduced into the composition to form surface alloyed magnesium metal particulates during the milling step.

In preparing the reaction mixture/composition, 500 g of 300μ MnO₂ (same as the MnO₂ disclosed in Example 1, procedure for Mg+MnO₂), 69.44 g of 500μ Mg (same as the Mg^(o) described in Example 1 procedure for Mg+MnO₂) and 5 g Zn^(o) particles, from Sigma Aldrich with a purity of 99.99%, were combined, placed in the VKE mill and milled for 6 hours. The remaining procedure is the same as that described in Example 1, procedure for Mg^(o)+MnO₂.

This inventor found that the milling process is effective for: (i) mixing the ingredients to form a homogeneous reactive composition; (ii) assures desired intimate electrical contact between the ingredients, i.e., Mg+MnO₂+Zn^(o) metal; (iii) is an effective means of forming surfaces alloyed with added metals, such as zinc, cobalt, nickel, iron, aluminum and mixtures of the same; and, (iv) also promotes better surface adhesion of the MnO₂ to the magnesium or alloyed magnesium.

Example 13

This example discloses a flameless heating composition of the invention comprising a combination of both oxides of manganese and ruthenium in a 30% RuO₂, 70% MnO₂ proportional range.

In preparing the composition, 48.61 g of 500μ Mg (same as disclosed in Example 1), 350 g of 300μ particle size of MnO₂ (same as the MnO₂ disclosed in Example 1 procedure for Mg+MnO₂) and 150 g RuO₂, 99.99% pure from Sigma Aldrich (12036-10-1), were combined, placed in the VKE mill and milled for 6 hours. The remaining procedure is the same as that described in Example 1.

Example 14

This example discloses a flameless heating composition of the invention similar to Example 13, except the combination of oxides of manganese and ruthenium have been reversed wherein RuO₂ is present in 70% range, and the MnO₂ is present in a proportional range of 30%.

In preparing the composition, 20.83 g of 500, Mg (same Mg disclosed in Example 1 and the procedure for milling Mg+MnO₂), 150 g of 300μ of MnO₂ (same MnO₂ disclosed in Example 1 and milling procedure for Mg+MnO₂ in Example 1) Mg, and 350 g RuO₂ (same as the RuO₂ described in Example 13, Mg+30% RuO₂+70% MnO₂), were combined, placed in the VKE mill and milled for 6 hours. The remaining procedure is the same as that disclosed in Example 1.

Example 15

This best mode example demonstrates a flameless heating composition of the invention comprising RuO₂ as the sole hydrogen suppressing agent.

In preparing the composition, 45.50 g of 500% Mg (same as the Mg disclosed in Example 1) and 500 g RuO₂, (same as the RuO₂ disclosed in Example 13), were combined, placed in the VKE mill and milled for 6 hours. The remaining procedure is the same as that described in Example 1.

Example 16

This example demonstrates a further embodiment of the invention wherein the flameless heater mixture includes in addition to Mg and MnO₂, 10% by-weight carbon to promote the rate of reaction and the generation of heat.

In preparing the reaction mixture/composition, 69.44 g of 500μ Mg (Same type of Mg disclosed in Example 1), 500 g MnO₂ (same as the MnO₂ disclosed in Example 1) and 50 g carbon from Cabot Corp., Boston, Mass., available under the trademark Vulcan XC72R, Lot: GP-3860 were combined and placed in the VKE mill and milled for 6 hours. The remaining procedure for this composition follows the same protocols as disclosed in Example 1, above.

Example 17

A further embodiment of the invention is presented wherein 1% Na₂S is introduced into the flameless heater composition Mg+MnO₂ composition as a hydrogen overvoltage suppressor. A metal sulfide may be incorporated into the composition as a fail safe in the event hydrogen is unexpectedly generated.

The flameless heater composition was prepared by mixing 69.44 g of 500% Mg (same Mg disclosed in Example 1), 500 g of MnO₂ (same MnO₂ disclosed in Example 1) and 5 g Na₂S (from Sigma Aldrich), and placing the mixture in the VKE mill and milling for 6 hours. The remaining procedure corresponds to that described in Example 1, above.

Example 18

Another embodiment of the flameless heater compositions of the invention includes the introduction of a filler/flowing agent, such as 2% SiO₂ to the magnesium/manganese dioxide.

This embodiment may be prepared by combining 69.44 g of 500% Mg (the same Mg disclosed in Example 1) with 500 g MnO₂ (the same MnO₂ disclosed in Example 1) and 10 g of 20μ SiO₂ (from Sigma Aldrich, purity=99.5%) and placing the mixture in the VKE mill and milling for 6 hours. The remaining procedure for preparing corresponds to that disclosed in Example 1.

Example 19

A similar flameless heater composition to that of Example 18 may be prepared using 2% CaCO₃ filler/flowing agent with the magnesium and manganese dioxide.

The reaction mixture/composition may be prepared by combining 69.44 g of 500% Mg (same Mg as disclosed in Example 1), 500 g MnO₂ (same MnO₂ as disclosed in Example 1) and 10 g of 20μ CaCO₃ (from Sigma Aldrich, purity=99.0%), and placing the mixture in the VKE mill and milling for 6 hours. The remaining procedure corresponds to that described in Example 1.

Example 20

A 99.98% pure magnesium powder of 200-300μ particle size from Superior Metal Powders and containing 60 ppm Al, 50 ppm Cu, 300 ppm Fe, 700 ppm Mn, 50 ppm Si, 50 ppm Zn and 80 ppm Sn was used in this test. The 70-80μ γ-MnO₂, from Tronox, LLC, with a purity of 99% and contained 1.2% SO₄ ²⁻, 2600 ppm Na, 190 ppm Al, 310 ppm C, 35 ppm Fe and 400 ppm K. These two materials were used to make a batch sample, in a stoichiometric ratio according to equation [1] above, along with 5% Asbury 4827 carbon, a synthetic graphite of <20-<30μ particle size, containing 1440 ppm Al, 865 ppm Ca, 2150 ppm Fe, 300 ppm Mg, 200 ppm Na and 2900 ppm Si.

Approximately 1100 g of a mixture containing 919.2 g MnO₂, 52.2 g C and 130 g Mg was weighed and placed in the Vibrokinetic Energy (VKE) Mill, from Microgrinding System, Inc., model 624 (diameter=6″ and tube length=24″). This mill is run with 36 stainless steel rods (6 with a diameter=1″, 30 with a diameter= 7/16″) with a length of 24″ as a stainless steel rod. The sample mixture is loaded into the mill via the 2″ diameter feed. All screws and openings are tightened and secured prior to running the mill for 1.5 hours. At the end of 1.5 hours, the sample is left in the mill for 20 minutes to cool. The sample is removed with a Nalgene scoop, transferred to a 1000 ml stainless steel beaker and stored in a desiccator with calcium sulfate as the dehydrating agent.

A Unilayer 270 bag material from Midwest Filtration is used to contain the milled Mg/MnO₂ mixture. First, the bag material is cut into a 16.5″×11″ sheet and folded in half to make a 8.25″×11″ bag. Prior to adding the sample, one of the 8.25″ sides and the 11″ side is heat sealed to form a pocket. The task is done with a Uline, 8″, Impulse Sealer (H-163). 450 g of the milled Mg/MnO₂ mixture is placed in the Unilayer Pocket and sealed closed. This completed ration heater is placed in a UGR-E tray, over which the 3500 g “water pouch” is placed. This assembly is placed in a card board box and then 350 ml of water is added. The card board box is then closed and the edges sealed with a tape. The temperature variation was recorded as a function of time over a 60 minute period, and is presented in FIG. 8. The results of the mixture of this Example is labeled “Present Invention”, while the results of a prior art mixture is labeled “Prior Art Example 3”.

While the invention has been described in conjunction with various embodiments, they are illustrative only. Accordingly, many alternatives, modifications and variations will be apparent to persons skilled in the art in light of the foregoing detailed description, and it is therefore intended to embrace all such alternatives and variations as to fall within the spirit and broad scope of the appended claims. 

1. A method for generating energy for flameless heating, which comprises the steps of: (i) forming a reaction mixture comprising at least magnesium or a magnesium-containing alloy, a hydrogen eliminator or suppressor, and (ii) reacting the reaction mixture of (i) by the step of introducing water or an electrolyte thereto to generate sufficient thermal energy for heating an article or substance while simultaneously eliminating or suppressing the generation of hydrogen.
 2. The method according to claim 1, wherein the hydrogen suppressor is a transition metal oxide.
 3. The method according to claim 2, wherein the transition metal oxide is an oxide of manganese or ruthenium.
 4. The method according to claim 1, wherein the magnesium-containing alloy comprises at least one alloying element selected from the group consisting of iron, cobalt, nickel, zinc, aluminum and mixtures thereof.
 5. The method according to claim 1, wherein the reaction mixture (i) further comprises at least one member selected from the group consisting of a hydrogen overvoltage suppressor, a promoter, a flowing agent and a reaction activator.
 6. The method according to claim 5, wherein the hydrogen overvoltage suppressor is a metal sulfide, a carbon and said promoter is a carbon particulate; said flowing agent is silica or calcium carbonate, and the reaction activator is a salt selected from the group consisting of sodium halide, magnesium halide and magnesium perchlorate.
 7. The method according to claim 5, wherein said reaction mixture (i) is formed by milling said magnesium or magnesium-containing alloy with said hydrogen eliminator or suppressor, and mixing said milled reaction mixture with said at least one member selected from the group consisting of said hydrogen overvoltage suppressor, promoter, flowing agent, and/or reaction activator prior to activating the heater reaction with water.
 8. A hydrogen suppressing, flameless, heat generating chemical composition comprising a reaction mixture having at least the following reactants: magnesium or a magnesium-containing alloy, a hydrogen suppressor and water, each of said reactants being present in a proportional amount to generate sufficient heat to heat water, medical supplies and/or consumable rations.
 9. The hydrogen suppressing, flameless, heat generating chemical composition according to claim 8, further comprising at least one member selected from the group consisting of a hydrogen overvoltage suppressor, a promoter, a flowing agent and a reaction activator.
 10. The hydrogen suppressing, flameless, heat generating chemical composition according to claim 8, wherein said magnesium alloy comprises at least one alloying member selected from the group consisting of iron, cobalt, nickel, zinc, aluminum and mixtures thereof.
 11. The hydrogen suppressing, flameless, heat generating chemical composition according to claim 8, wherein said hydrogen suppressor comprises oxides of manganese and/or ruthenium.
 12. The hydrogen suppressing, flameless, heat generating chemical composition according to claim 11, wherein said oxide of manganese is γ-MnO₂ or β-MnO₂.
 13. The hydrogen suppressing, flameless, heat generating chemical composition according to claim 11, wherein the oxide of manganese is present in an amount ranging from 0.5 to about 10 times the stoichiometric amount required for the magnesium and the oxide of manganese reaction with water to occur.
 14. The hydrogen suppressing, flameless, heat generating chemical composition according to claim 9, wherein the hydrogen overvoltage suppressor is a metal sulfide, the promoter is a carbon, and the activator is an inorganic salt.
 15. The hydrogen suppressing, flameless, heat generating composition according to claim 9, wherein the reaction activator is magnesium chloride present in an amount from about 0.001 to about 50 percent by-weight.
 16. The hydrogen suppressing, flameless, heat generating composition according to claim 15, wherein the reaction activator is mixed with milled magnesium-manganese dioxide mixtures prior to activating the heater reaction with water.
 17. The hydrogen suppressing, flameless, heat generating composition according to claim 9, wherein the reaction activator is a thermally and electrically conducting, high surface area synthetic graphite present in an amount from about 0.001 to about 50 percent by-weight.
 18. The hydrogen suppressing, flameless, heat generating composition according to claim 17, wherein the synthetic graphite is Asbury
 4827. 19. The hydrogen suppressing, flameless, heat generating composition according to claim 9, wherein the reaction activator is a conducting carbon present in an amount from about 0.001 to about 50 percent by-weight.
 20. The hydrogen suppressing, flameless, heat generating composition according to claim 19, wherein the conducting carbon is Ketjenblack, Black Pearls® 2000, Black Pearls® 1300 or Asbury TC
 307. 21. The hydrogen suppressing, flameless, heat generating composition according to claim 9, wherein the reaction activator is a conducting graphite or carbon present in an amount from about 0.001 to about 50 percent by-weight and the reaction activator is mixed with a magnesium-manganese dioxide mixture in a vibratory or ball mill for at least an hour.
 22. A heater device comprising the hydrogen suppressing, flameless, heat generating chemical composition according to claim
 8. 23. The heater device of claim 22 wherein the hydrogen suppressing, flameless, heat generating chemical composition is enclosed within a bag comprising a filter cloth, wherein said filter cloth comprises a 6-ply sonic bonded polypropylene laminate.
 24. The heater device of claim 22 wherein the hydrogen suppressing, flameless, heat generating chemical composition is enclosed within a dual layer bag comprising a first layer comprising polyester fibers and a second layer comprising polypropylene fibers.
 25. The heater device of claim 22 wherein the hydrogen suppressing, flameless, heat generating chemical composition is enclosed within a multi-layer bag comprising a plurality of layers of polyester fibers.
 26. The heater device of claim 22 wherein the hydrogen suppressing, flameless, heat generating chemical composition is enclosed within a dual layer bag comprising an outer layer of 3-ply bonded polypropylene fiber cloth and an inner layer of spunbond/meltblown/spunbond filter media comprising polypropylene.
 27. A meal, ready-to-eat package comprising the flameless heater device according to claim
 22. 